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Clusters of the transition metals were generated by laser vaporisation of a sample of the metal into the throat of a pulsed supersonic expansion. This allowed clusters with internal temperatures as low as 5 K to be routinely prepared. Mass-selective detection was accomplished by multi-photon ionisation of the clusters within the ion source of a time - of - flight mass spectrometer. Use of a tunable laser to carry out electronic excitation, prior to ionisation, allowed mass - resolved resonant two - photon ionisation spectra of the clusters to be recorded. Real time control of the experiment and automated data logging was achieved using software developed to run on an IBM PC - AT microcomputer. This allowed multiple ion signals to be recorded simultaneously whilst carrying out R2PI or time-resolved studies on the metal cluster species in the beam. Resonant two - photon ionisation spectroscopic studies were carried out on the ( 0 - 0 ) and ( 1 - 0 ) bands of the J X system of Cu9 and the A X system of Ag->. The 0.04 cm-1 bandwidth of the tunable dye laser used allowed rotationally resolved spectra to be recorded. The spectra recorded for these systems showed them both to be AA = 0 ( or AS2 = 0 ) transitions. The J state of CU2 was assigned to the 1 Zj state derived from the ?P + atomic limit at Dg(X) + 45821 cm-1. Rotational analysis of the spectra yieldedl | lthe following constants for the Cu2 isotopomer: Bg = 0.1166(1) cm , ae = 0.0021(1) cm-1. This gave Rg = 2.138(1) A for the J state, shorter than the ground state bond length. Accordingly the transition was assigned to 3ditg -*?4piru, to give the above assignment. The rotational constants obtained, for the *?7Ag-, isotopomer, from analysisI _ | *of the spectra of the A X system of Ag-, were: Bg = 0.0447(3) cm , ae= 0.0004(2) cm'*, and Bq = 0.0490(18) cm"1. These gave bond lengths of Rg = 2.649(9) A and Rq = 2.530(46) A. The observed Ail = 0 transition agreed with the previous assignment of the A state as 0* arising from the 5sag -+ 5sau promotion.

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A range of computational and experimental techniques have been applied to the study of four metal cluster systems. Decorated rhodium clusters Rh n O m (N 2 O) + ( n = 4 − 8, m = 0 − 2) have been investigated both experimentally by IR-MPD and computationally using DFT. The effect of cluster size as well as oxygen coverage on the spectroscopy of the N 2 O bend are analyzed. The infrared-induced decomposition of N 2 O on Rh n O + m is observed on all cluster sizes, with marked differences as a function of size and oxygen coverage, particularly in the case of Rh 5 (N 2 O) + . The oxidation of CO was studied on the surface of small platinum cluster cations Pt n O + m ( n = 3 − 7, m = 2 , 4) by IR-MPD at 400 – 2100cm −1 . Spectroscopically, oxygen is found to be bound both dissociatively and molecularly on the cluster surface, while the CO band is found to red shift in cluster size, and blue shift with oxygen coverage. Oxidation of CO proceeds on all cluster sizes, with a constant branching ratio of 40% : 60% . DFT calculations identified key stationary points and barriers on the Pt 4 O 2 CO + reaction pathway. The one-colour Ta 2 photodissociation is studied by photoionization and VMI in the range 23500 – 24000cm −1 , finding clear evidence of a fragmentation process producing Ta , which is interpreted as fragmentation of cationic Ta + 2 at the two photon level. A majority of the observed channels produce either atomic ( Ta( 4 F 3/2 ) ) or cationic ( Ta + ( 5 F 1 ) ) ground state. An improved value for the dissociation energy D 0 ( Ta + 2 ) is obtained, in agreement with computational predictions. The anisotropies observed show weak evidence of a perpendicular transition being involved in the photodissociation process. Finally, the photodissociation dynamics of Cu 2 are studied by spectroscopy in the range 36000 – 38200cm −1 as well as VMI. Clear evidence for resonant photolysis of Cu 2 is obtained, as a result of both direct dissociation of the Cu + 2 2 Π ion state as well as dissociation of doubly excited Cu 2 states, which leads to a determination of dimer dissociation energies. Finally, the production of Cu + 2 is interpreted as evidence of photolysis of Cu 3 , from which a Cu 3 dissociation energy is derived.

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